JPH07261303A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic emulsion capable of forming photographic sensitive material high in sensitivity and superior in graininess and improved in pressure resistance and a photographic sensitive material using this emulsion. CONSTITUTION:This silver halide photographic emulsion contains flat silver halide grains occupying >=50% of the projection areas of the total silver halide grains and these grains have a laminar structure substantially parallel to the principal crystal plane and >=50% of these flat grains have >=10 dislocation lines, and the photosensitive material is formed by using this emulsion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion which gives a photographic light-sensitive material having improved sensitivity, graininess and pressure resistance, and a silver halide photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art The spread of photography equipment such as cameras has been increasing in recent years, and the opportunity for photography using silver halide photographic light-sensitive materials has been increasing. Along with this, demands for higher sensitivity and higher image quality of silver halide photographic light-sensitive materials are also increasing.

[0003] One of the dominant factors for high sensitivity and high image quality of silver halide photographic light-sensitive materials is silver halide grains, and silver halide grains aiming at higher sensitivity and higher image quality Particle development has traditionally been pursued in the industry.

However, as is generally done, when the grain size of silver halide grains is reduced in order to improve the image quality, the sensitivity tends to decrease, and both high sensitivity and high image quality are satisfied. There was a limit.

A technique for improving the sensitivity / size ratio per silver halide grain is being researched in order to further improve the sensitivity and the image quality. One of them is a tabular silver halide grain. The technology of using is Japanese Patent Laid-Open No. 58-111935
Issue 58-111936, Issue 58-111937, Issue 58-113927,
No. 59-99433, etc. When these tabular silver halide grains are compared with so-called normal crystal silver halide grains such as octahedron, tetradecahedron or hexahedron, when the volume of silver halide grains is the same, the surface area is large and therefore Since many sensitizing dyes can be adsorbed on the surface of silver particles, there is an advantage that higher sensitivity can be achieved.

Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside a tabular silver halide grain, and JP-A-63-151618 discloses a hexagonal tabular silver halide grain. JP-A-63-163451 adopts a technique of using tabular silver halide grains in which the ratio of grain thickness to the longest distance between twin planes is 5 or more. The effect on sex is shown.

Further, JP-A-63-106746 discloses a tabular silver halide grain having a substantially layered structure in a direction parallel to two principal planes facing each other. Has a layered structure divided by planes substantially parallel to the two opposing main planes, and the average silver iodide content of the outermost layer is the average silver iodide content of the entire silver halide grain. The techniques using tabular silver halide grains each having at least 1 mol% higher than the above are described. In addition, JP-A-1-183644 discloses a technique using tabular silver halide grains characterized in that the silver iodide containing silver iodide has a completely uniform silver iodide distribution.

[0008]

However, these conventional techniques have a limit in achieving both high sensitivity and high image quality.
This is insufficient for obtaining the sensitivity and image quality required in recent light-sensitive materials, and the development of more superior technology is desired.

On the other hand, in handling the silver halide photographic material in photographing, developing, etc., improvement in resistance to various pressures that are accidentally or inevitably applied is desired in terms of stability of photographic performance. There is.

Conventionally, as means for improving pressure resistance, for example, US Pat. No. 2,628,167, JP-A Nos. 50-116025 and 51-1.
No. 07129 describes a method of adding an iridium salt or a thallium salt at the time of forming silver halide grains. However, these methods have a problem that the sensitivity is lowered.

Further, in JP-A-1-183644, a tabular plate containing a silver halide phase of 3 mol% or more of silver iodide and having a completely uniform silver iodide distribution of the silver halide containing the silver iodide. Although a method of using a silver halide emulsion containing granular silver halide grains has been disclosed, it is far insufficient in response to the demand for further improvement in pressure resistance in recent years.

Further, a technique is known in which a plasticizer and other additives are added to the silver halide emulsion to be used to change the physical properties of a binder for dispersing silver halide grains,
For example, in JP-A-2-135335, the glass transition temperature is
A method of using a latex consisting essentially of a methacrylate polymer below 50 ° C. and an emulsion containing tabular silver halide grains is disclosed. However, this method is not a preferable method because it involves changes in other photographic performances due to changes in the physical properties of the binder, and the effect is not satisfactory, and the development of superior technology is desired. .

With respect to dislocation lines, there is a conventional method, for example, Japanese Patent Laid-Open No. 63-2
In No. 20238, an example using a silver halide emulsion containing tabular silver halide grains in which the number of dislocation lines is specified is
In JP-A-3-175440, an example of using a silver halide photographic emulsion containing tabular silver halide grains in which dislocations are concentrated near the apex of the grain is taken up. It is insufficient as a technique for controlling dislocation lines on the plane.

Therefore, an object of the present invention is to provide a silver halide photographic emulsion which provides a photographic light sensitive material having high sensitivity, excellent graininess and improved pressure resistance, and a silver halide photographic light sensitive material using the same. It is in.

[0015]

The above objects of the present invention have been achieved by the constituent elements described below.

(1) In a silver halide photographic emulsion containing silver halide grains and a dispersion medium, the silver halide grains contained in the silver halide photographic emulsion are tabular silver halide grains, and the tabular grains are The silver halide grains have a layered structure substantially parallel to the principal plane, and 50% or more (number) of the tabular silver halide grains have 10 dislocation lines per grain.
A silver halide photographic emulsion containing silver halide grains, characterized in that it has one or more.

(2) The silver halide photographic emulsion as described in the above item (1), wherein the tabular silver halide grains have two twin planes substantially parallel to the principal plane.

(3) The silver halide photographic emulsion as described in the above item (2), wherein the tabular silver halide grains are monodisperse.

(4) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the above (1), (2) or (3). ) A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion as described in any one of 1) to 10) above.

The present invention will be described in more detail below.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are tabular silver halide grains.
The tabular silver halide grains are crystallographically classified as twins.

A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the article Photographic Correspondents. (Photographishe Korrespondenz)
Volume 99, page 99, volume 100, page 57.

In the present invention, the proportion of tabular silver halide grains in the total projected area of silver halide grains is preferably 50% or more, more preferably 60% or more, and most preferably 70% or more.

In the tabular silver halide grain in the present invention, the average value of the ratio of grain size to grain thickness (also referred to as aspect ratio) is preferably 1.3 or more and less than 5.0, more preferably 1.5 or more and less than 4.5, and further It is more preferably 2.0 or more and less than 4.0. The average aspect ratio is obtained by averaging the ratio of grain size to thickness of all tabular grains.

In the present invention, the tabular silver halide grain having two twin planes substantially parallel to the principal plane means that all tabular silver halide grains have two twin planes parallel to the principal plane. It means that the ratio of silver halide grains contained is 60% or more (number).

The tabular silver halide grain in the present invention preferably has two twin planes parallel to the main plane, and more preferably the tabular silver halide grain has two twin planes parallel to the main plane. The ratio of silver halide grains
60% or more (number), more preferably 70% or more,
Most preferably, it is 80% or more.

The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First,
A silver halide photographic emulsion is coated on a support so that the main planes of the tabular silver halide grains contained therein are oriented substantially parallel to the support to prepare a sample. This is cut with a diamond cutter to obtain a thin section with a thickness of about 0.1 μm. The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

The average grain size of the tabular silver halide grains of the present invention is preferably 0.1 μm or more and 5.0 μm or less, more preferably
0.2 μm or more and 4.0 μm or less, most preferably 0.3 μm or more and 3.0
It is less than μm.

In the present invention, the average particle size is defined as the particle size ri when ni × ri ³ between the frequencies ni and ri ^{3 of} particles having the particle size ri is maximum. (3 significant figures, rounding down to the nearest 4) (The number of measured grains is indiscriminately 1,000 or more.) The grain size ri here is the tabular silver halide grain. Is the diameter when a projected image when viewed from a direction perpendicular to the main plane is converted into a circular image of the same area.

The grain size ri can be obtained by enlarging tabular silver halide grains with an electron microscope at a magnification of 10,000 to 70,000 and measuring the grain diameter on the print or the area at the time of projection. it can. Further, the thickness of tabular silver halide grains can be determined by actually measuring the thickness of grains in a direction parallel to the principal plane on a similarly photographed print.

The silver halide photographic emulsion according to the present invention may be any one such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution, but a monodisperse emulsion is preferred.

A monodisperse emulsion means that when the breadth of the distribution is defined by the breadth of the distribution (%) = (standard deviation / average grain size) × 100, the breadth of the distribution is 20%.
It is the following, and more preferably 15% or less.

The average particle diameter and standard deviation are obtained from the particle diameter ri defined above.

For the silver halide photographic emulsion of the present invention, any silver halide such as silver iodobromide, silver iodochloride, silver chloroiodobromide and the like used in ordinary silver halide emulsions can be used. However, silver iodobromide and silver chloroiodobromide are particularly preferred.

The silver halide grain contained in the silver halide photographic emulsion of the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly formed inside the grain. Good.

In the present invention, when silver iodobromide is used,
The silver iodide content is preferably 2 mol% or more and 15 mol% or less, more preferably 3 mol% or more and 12 mol% or less, as the average silver iodide content in the entire silver halide grains. It is particularly preferably 4 mol% or more and 12 mol% or less.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are so-called core / shell type grains in which silver halide phases having different silver iodide contents are stacked in layers in the direction perpendicular to the principal plane. It may be. It is preferable that the core and the shell have different silver iodide contents.

The silver iodide content of the core is preferably 5 mol% or more and the solid solution limit or less, more preferably 10 mol% or more and the solid solution limit or less. The silver iodide content of the outermost shell of the above shells, that is, the shell that usually forms the outermost surface layer is preferably 5 mol% or less. The proportion of the core is preferably 2 to 60% of the volume of the whole particle, more preferably 5 to 50%.

In the present invention, the solid solution limit is represented by the maximum mol% of iodide which can exist as a solid solution in silver halide. Specifically, TH James edition The Theory of Photo
Graphic Process 4th Edition (published by Macmillan), can be determined by the method described on page 4. In the case of silver iodobromide, I _MAX (mol%) = 34.5 + 0.165 (t-25) (t is It can be calculated by the temperature (Celsius).

The tabular silver halide grains contained in the silver halide photographic emulsion of the present invention have a layered structure substantially parallel to the principal plane. In the present invention, the term "consisting of a layered structure substantially parallel to the principal plane" means that the tabular silver halide grains have a circle-equivalent diameter of a projected area in the direction perpendicular to the principal plane at the time when 50% of the silver halide volume is formed. And the diameter of the circle equivalent to the projected area in the direction perpendicular to the main plane of the finally obtained tabular silver halide grains is substantially the same. More specifically, the final flat plate obtained is the average of the circle-equivalent diameters of the projected area from the direction perpendicular to the principal plane of the tabular silver halide grains when 50% of the silver halide volume is formed. The average rate of change of the circle-equivalent diameter of the projected area from the direction perpendicular to the main plane of the regular silver halide grains is within 5%, preferably within 3%, particularly preferably 1
% Is within.

The rate of change of the circle-equivalent diameter was measured by an electron microscope for the tabular silver halide grains at the time when 50% by volume of the silver halide was formed and the tabular silver halide grains finally obtained. The equivalent circle diameter of the projected area from the direction perpendicular to the main plane is measured for each of 1,000 or more and averaged, and when the former is A and the latter is B, it can be determined by the following formula.

[(B−A) / A] × 100 = Average rate of change in equivalent circle diameter (%) In the present invention, the tabular silver halide grain passes through the center of the silver halide grain and is divided into two parallel grains. For silver halide phases other than the area occupied by the tabular base silver halide grains on the fault plane perpendicular to the principal plane, the silver halide composition at any distance from the principal plane is substantially in the direction parallel to the principal plane. It is preferable that they are the same. More specifically,
The silver halide photographic emulsion of the present invention is gelatinized with proteolytic oxygen, and then the tabular silver halide grains contained in the silver halide photographic emulsion are embedded in methacrylic resin, and a slice having a thickness of 800 Å is cut with a diamond cutter. To create. A tabular substrate was obtained by a point analysis using the EPMA method well known in the art for a tabular silver halide grain in which a cross-sectional layer passing through the grain center and perpendicular to two parallel principal planes was obtained on the section. In the area other than the area occupied by the silver halide grains, when the silver halide composition is measured at 5 points or more at equal intervals including the both ends of the grain in directions parallel to the main plane at arbitrary distances from the main plane, It is preferable that the difference in content of silver halide or silver chloride is 1 mol% or less.

In the present invention, the tabular base silver halide grain means the tabular silver halide grain forming process of the tabular silver halide grain contained in the silver halide photographic emulsion of the present invention.
A silver halide grain formed immediately before the start of growth to form a layered structure parallel to the principal plane, and accounts for 50% or less by volume of the silver halide grain contained in the silver halide photographic emulsion of the present invention. Is preferably within 40%, more preferably within 30%.

In the production of the silver halide photographic emulsion of the present invention, the dispersion medium means a substance capable of forming a protective colloid such as gelatin. In the present invention, when gelatin is used as the dispersion medium, the gelatin may be lime-treated or acid-treated. Details of the method for producing gelatin are described in "The Macromolecular Chemistry of Gelatin" by Arthur Weiss (Academic Press, 1964). Examples of substances that can form protective colloids other than gelatin include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and cellulose such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate. Derivatives, sugar derivatives such as sodium alginate, starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-n-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, etc. There may be mentioned various synthetic or semi-synthetic hydrophilic polymeric substances such as polymers. In the present invention, it is preferable to use gelatin as the dispersion medium.

The dislocation lines of the tabular silver halide grains according to the present invention are, for example, JF Hamilton, Phot.Sci.Eng., 11, 57 (1
967), T. Shiozawa, J.Soc.Phot.Sci.Japan, 35, 213 (1
It can be observed by a direct method using a transmission electron microscope at low temperature described in 972). That is, the silver halide grains taken out carefully so as not to apply pressure to the grains causing dislocations on the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beam In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to observe more clearly using a high-voltage electron microscope (200 KV or more for particles with a thickness of 0.25 μm). .

The position and number of dislocations of each grain can be determined from the photograph of the grain obtained by such a method.

The position of the dislocation line of the tabular silver halide grain according to the present invention is preferably in the region of 0.58 L to L from the center of the silver halide grain toward the outer surface. It is preferably generated in the region of 0.70 L to 0.98 L. The direction of the dislocation line is approximately from the center to the outer surface, but it often meanders.

In the present invention, the center of a silver halide grain means that silver halide microcrystals are dispersed in a methacrylic resin in the same manner as in the method described in Inoue et al. Then, solidify it, make it into an ultrathin section with a microtome, and pay attention to the section sample with the maximum cross-sectional area and the cross-sectional area of 90% or more, and draw the circumscribed circle that is the minimum with respect to the section. It is the center of the circle when.

In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point that intersects the outer circumference of the particle when a straight line is drawn from the center of the circle to the outside.

The tabular silver halide grains according to the present invention are
The ratio of the number of dislocation lines per grain being 10 or more is 50% or more (number), more preferably 60% or more, further preferably 70% or more, and most preferably 1 grain The ratio of dislocation lines being 20 or more is 70% or more (number).

In the present invention, the number of dislocation lines in the silver halide grain is 10 or more, preferably 20 or more and 10,000 or less, per silver halide grain. It is difficult to confirm the number of regions in the area of more than 10,000 and the photographic characteristics are not improved.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are preliminarily prepared by allowing an aqueous solution containing a protective colloid and seed grains, if necessary, to be present in a reaction vessel in advance. It is obtained by supplying silver halide fine grains to form silver halide nuclei and then crystal-growing or seed-crystal growing, but seed-grains are preferably used. Here, the seed particles can be prepared by a single jet method, a controlled double jet method or the like well known in the art. The halogen composition of the seed grains is arbitrary and may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. Silver bromide and silver iodobromide are preferred.

The seed particles used in the present invention may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or an irregular crystal form such as a sphere or a plate. It may be one. In these particles, {100} planes and {111} planes
Any surface ratio can be used. Further, those having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed, but it is preferable to use twin seed particles described in Japanese Patent Application No. 3-341164.

As the means for forming the silver halide photographic emulsion according to the present invention, various methods well known in the art can be used. That is, the single jet method,
The double jet method, the triple jet method and the like can be used in any combination.

The silver halide photographic emulsion of the present invention can be produced by any of the acidic method, the neutral method and the ammonia method, but it is preferable to use the acidic method or the neutral method, most preferably the neutral method. Method is used.

In the production of the silver halide photographic emulsion of the present invention, the halide ion and the silver ion may be mixed at the same time, or while either one is present, the other may be mixed. Further, while considering the critical growth rate of silver halide crystals, halide ions and silver ions may be grown successively or simultaneously while controlling pAg and pH in the mixing vessel. The conversion method may be used to change the silver halide composition of the grains at any step of the silver halide formation. Further, halide ions and silver ions may be supplied as fine silver halide particles into the mixing vessel.

In the present invention, in the tabular silver halide grains, the layered structure parallel to the principal plane has a tabular shape having substantially the same projected area as that of the tabular silver halide grains finally obtained. After the silver halide grains of the base of No. 3 are grown mainly in the lateral direction, the growth after that is almost only in the main plane direction. It is obtained by appropriately selecting and growing while confirming the formation of a layered structure parallel to.

In the production of silver halide grains in the present invention, the concentration and growth of an additive solution containing halide ions, silver ions or silver halide fine particles in grain growth
It is important to select pAg, gelatin concentration in the aqueous solution in which silver halide grains are grown, growth temperature, and the like. The concentration of the additive liquid containing halide on and silver ions is preferably 0.5 to 4 mol / l, more preferably 1.5 to 3.5 mol / l. The concentration of the addition liquid containing fine silver halide grains is preferably 0.3 to 2.0 mol / l, more preferably 0.5 to 1.5 mol / l.

The growth pAg is preferably from 10.5 to 8.6 at the time of forming the base silver halide grains, whereby the tabular silver halide grains can be grown mainly in the lateral direction, and the growth after the formation of the tabular base silver halide grains is increased. PAg 8.4 ~ 6.
On the tabular substrate silver halide grains by carrying out in 8,
A layered structure can be formed in the direction perpendicular to the main plane.

The gelatin concentration is preferably 0.5-40%. It is better to increase the gelatin concentration at the time of grain growth after that compared with the time of forming tabular tabular silver halide grains. The growth temperature is preferably 60 to 90 ° C, more preferably 70 to 80 ° C.
In the present invention, the addition of an aqueous solution containing silver ions, halide ions or silver halide fine particles in the growth after the formation of the base silver halide grains is closer to the critical growth rate to the extent that small grains are less likely to form a layered layer. It favored the formation of the structure.

In the production of the silver halide photographic emulsion of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like can be present, but when forming a layered structure of tabular silver halide grains, these are used. It was more advantageous not to exist or to deactivate the silver halide solvent of.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salt is formed in the process of forming and / or growing the grain. Including), rhodium salt (including complex salt), iron salt (including complex salt), etc., can be added to the metal ion to allow these metal elements to be contained inside the particle and / or on the surface of the particle. By placing in such a reducing atmosphere, reduction sensitizing nuclei can be imparted to the inside and / or the surface of the grain.

In the silver halide photographic emulsion of the present invention,
In order to introduce dislocations into the silver halide grains, for example, a method of providing a specific high iodine phase inside the silver halide grains can be used. In this case, the high iodine phase is silver iodide,
Silver iodobromide and silver chloroiodobromide are preferable, silver iodide or silver iodobromide is more preferable, and silver iodide is particularly preferable.

As a method for this, for example, a conversion method by adding an iodide salt alone, or, for example, JP-A-58-58
-108526, 59-133540 and 59-162540 may be used.

When the conversion method is carried out by adding iodide salt alone, the addition amount of iodide salt is preferably 10 ^-6 to 10 ^-1 mol per mol of silver halide, more preferably 3 ×.
It is 10 ^{−5 to} 3 × 10 ⁻² mol. The addition can be performed using a funnel or a pump, but the addition time is preferably within 10 minutes, more preferably within 5 minutes. The timing of addition can be arbitrarily set according to the position where the dislocation line is desired to be introduced.

The tabular base silver halide grain in the present invention preferably has a silver halide volume of 50% or less, more preferably 40% or less, and most preferably 30% or less.

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may remain contained. When removing the salts, Research Disclosure (Re
search Disclosure (hereinafter abbreviated as RD) can be performed based on the method described in Item 17643, Item II.

Conditions other than those mentioned above in the production of the silver halide photographic emulsion according to the present invention are described in JP-A-61-6643.
No. 61, No. 61-14630, No. 61-112142, No. 62-157024,
62-18556, 63-92942, 63-151618, 63-1634
The optimum conditions can be selected by referring to known methods such as No. 51, No. 63-220238 and No. 63-311244.

The silver halide photographic emulsion of the present invention can be preferably used in a silver halide photographic light-sensitive material, more preferably a silver halide color photographic light-sensitive material.

When a color photographic light-sensitive material is constructed using the silver halide photographic emulsion of the present invention, the silver halide photographic emulsion used is one that has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No.17643, No.18716 and N.
o.308119 (hereinafter RD17643, RD18716 and RD3081 respectively
(Abbreviated as 19)). The following shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Silver halide of the present invention Known photographic additives which can be used when a color photographic light-sensitive material is constituted by using a photographic emulsion are also described in the above Research Disclosure.
Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity preventing agent 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25 to 26 Light absorber 1003 VIII 25 to 26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25 to 26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators / coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developer (included in light-sensitive material) Item 1011 XXB Color photographic light-sensitive using silver halide photographic emulsion Various couplers can be used in constructing the material, specific examples of which are described in Research Disclosure above.

The following are relevant description points.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC to G item Magenta coupler 1001 VII-D item VIIC to G item Cyan coupler 1001 VII-D item VIIC to G item Colored coupler 1002 Item VII-G Item VIIG Item DIR coupler 1001 Item VII-F Item VIIF Item BAR coupler 1002 Item VII-F Other useful residues Release coupler 1001 Item VII-F Alkali-soluble coupler 1001 Item VII-E Silver halide photograph of the present invention Additives used in constructing a color photographic light-sensitive material using an emulsion can be added by the dispersion method described in RD308119XIV.

When a color photographic light-sensitive material is constructed using the silver halide photographic emulsion of the present invention, the above-mentioned RD17643 28 is used.
The supports described on page RD18716 pp. 647-8 and RD308119 XVII can be used.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above-mentioned item RD308119VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above item RD308119VII-K.

The silver halide photographic emulsion of the present invention is a color negative film for general use or movies, a color reversal film for slides or televisions, color paper,
It can be preferably applied to various color photographic light-sensitive materials represented by color positive films and color reversal papers.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described in RD17643, pages 28 to 29, RD18716 61.
Development can be carried out by a usual method described on page 5 and XIX of RD308119.

[0080]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of Twinned Crystal Emulsion (TEm-1)) A seed having two parallel twin planes was prepared by the following method with reference to the description of Japanese Patent Application No. 3-341164. An emulsion (TEm-1) was prepared.

Solution A Ossein gelatin 80.0 g Potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution 0.48 ml Water 8000 ml solution B Silver nitrate 1200 g Water 1600 ml solution C Ocein gelatin 32.2 g Potassium bromide 790 g Potassium iodide 70.34 g Water 1600 ml solution D Ammonia water 470 ml The stirring device described in JP-A-62-160128 is used. The solution B and the solution C were added to the solution A stirred at 40 ° C. at a stirring speed of 1000 rpm for 7 minutes by the double jet method,
Nucleation was performed. During this period, pBr was kept at 1.60 to 1.70.

Thereafter, the temperature was lowered to 20 ° C. over 35 minutes. Furthermore, the solution D was added over 2 minutes, and then the mixture was aged for 5 minutes.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. The average grain size of this seed emulsion grain is 0.225
It was μm.

(Preparation of Comparative Emulsion (Em-1)) A comparative emulsion (Em-1) containing core / shell type tabular silver halide grains was prepared using the following 6 kinds of solutions.

Solution E-1 ossein gelatin 66.5 g distilled water 3323 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution 1.25 ml solution F-1 3.5N silver nitrate aqueous solution G-1 3.5N potassium bromide aqueous solution containing 4.0% by weight gelatin H-1 3.1% by weight gelatin and silver iodide grains (average particle size 0.05 μm) 1.175 mol of fine grain emulsion consisting of is shown below. To 1098 ml of a 5.0% by weight gelatin solution containing 0.028 mol of potassium iodide, 335 ml of an aqueous solution containing 1.175 mol of silver nitrate and 1.160 mol of potassium iodide were added over 35 minutes. The temperature was controlled at 40 ° C.

Solution J Potassium bromide 1.75N aqueous solution Necessary amount Solution K type emulsion (TEm-1) 0.130 moles It was kept at 75 ° C. in a reaction vessel which was vigorously stirred using the stirring device described in JP-A-57-92523. After the solution K was added to the solution E-1, the solution F-1, the solution G-1, and the solution H-1 were added by the simultaneous mixing method for 192 minutes.

Here, the addition rates of the solution F-1 and the solution G-1 were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and the generation other than the growing seed crystal and the distribution due to Ostwald ripening were observed. It was added at an appropriate addition rate so as not to cause deterioration. Solution H vs. Addition Rate of Solution F-1
-1 addition rate ratio is set so that a silver halide phase having the silver iodide content (mol%) shown in Table 1 is formed, whereby a core / shell type tabular halide having a multiple structure is formed. A silver halide photographic emulsion containing silver grains was prepared.

During the growth of silver halide grains, pAg was controlled as shown in Table 1 by appropriately using solution J.

After grain formation, desalting treatment is performed by a conventional method,
After that, gelatin is added and redispersed, and the pH is 5.80 and pAg at 40 ° C.
Was adjusted to 8.0.

The pAg and pH were measured by a conventional method using a silver sulfide electrode and a glass electrode.

[0092]

[Table 1]

(Preparation of Comparative Emulsion (Em-2)) A comparative emulsion (Em-2) containing core / shell type tabular silver halide grains was prepared using the following seven kinds of solutions.

Solution E-2 ossein gelatin 66.5 g distilled water 3323 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution 0.625 ml solution F-2 3.5N silver nitrate aqueous solution G-2 3.5N potassium bromide aqueous solution containing 4.0% by weight gelatin H-2 3.1% by weight gelatin and silver iodide grains (average particle size 0.05 μm) The method for preparing 0.913 mol of a fine grain emulsion consisting of is shown below.

5.0% by weight containing 0.022 mol of potassium iodide
To 862 ml of the gelatin solution (2), 260 ml each of an aqueous solution containing 0.913 mol of silver nitrate and 0.901 mol of potassium iodide was added over 35 minutes. The temperature was controlled at 40 ° C.

Solution J Potassium bromide 1.75N aqueous solution Required amount Solution K-2 type emulsion (TEm-1) 0.130 mol To 75 ° C. in a reaction vessel which was vigorously stirred using the stirring device described in JP-A-57-92523. Solution E-2 kept in solution K-2
After adding, solution F-2, solution G-2 and solution H-
2 was added by the double jet method over a period of 191 minutes.

Here, the addition rates of the solution F-2 and the solution G-2 were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and generation other than the growing seed crystal and distribution due to Ostwald ripening It was added at an appropriate addition rate so as not to cause deterioration. Solution H vs. Addition Rate of Solution F-2
-2 addition rate ratio is set so that a silver halide phase having a silver iodide content (mol%) shown in Table 2 is formed, whereby a core / shell type tabular halide having a multiple structure is formed. A silver halide photographic emulsion containing silver grains was prepared.

During the growth of silver halide grains, pAg was controlled as shown in Table 2 by appropriately using solution J.

After the formation of particles, desalting treatment is carried out by a conventional method,
After that, gelatin was added and redispersed, and the pH was adjusted to 5.80 and p at 40 ° C.
Adjusted Ag to 8.0.

The pAg and pH were measured by a conventional method using a silver sulfide electrode and a glass electrode.

[0101]

[Table 2]

(Preparation of Emulsion (Em-3) of the Present Invention) In the preparation of the comparative emulsion (Em-2), the following solution E-3 was used in place of the solution E-2, and the addition amount of silver was 15.0%. At the time point, the following solution L-3 was added for 30 seconds, and the solution H-2 was added to the addition rate of the solution F-2 during the silver halide grain growth.
An emulsion (Em-3) of the present invention was prepared in exactly the same manner except that the ratio of the addition rate of 2, the addition time, pAg and the like were controlled as shown in Table 3.

Solution E-3 Oscein gelatin 190.0 g Distilled water 9494 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution 0.625 ml Solution L-3 emulsion (Em-2) Aqueous solution containing 0.01 mol potassium iodide per mol 200 ml

[0104]

[Table 3]

(Preparation of Emulsion (Em-4) of the Present Invention) The following solution E-4 was used in place of the solution E-1 in the preparation of the comparative emulsion (Em-1), and the solutions F-1 and G- The following solutions F-4 and G-4 were used instead of 1, and the following solution L-4 was added in 30 seconds when the amount of added silver was 15.0%.
Further, the ratio of the addition rate of the solution H-2 to the addition rate of the solution F-4 during the silver halide grain growth and the addition time, pAg
An emulsion (Em-4) of the present invention was prepared in exactly the same manner except that the above were controlled as shown in Table 4.

Solution E-4 ossein gelatin 95.0 g distilled water 4747 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution 1.25 ml solution F-4 3.0N silver nitrate aqueous solution G-4 3.0N potassium bromide aqueous solution containing 4.0% by weight of gelatin L-4 emulsion (Em-1) 0.01 mol of potassium iodide per mol 200 ml of aqueous solution

[0107]

[Table 4]

(Preparation of Emulsion (Em-5) of the Present Invention) The following solution E-5 was used in place of the solution E-1 in the preparation of the comparative emulsion (Em-1), and the addition amount of silver was 15.0%. The following solution L-5 was added in 1 minute, and the ratio of the addition rate of the solution H-2 to the addition rate of the solution F-1 during silver halide grain growth, addition time, pAg, etc. are shown in Table 5. The emulsion of the present invention (Em
-5) was prepared.

Solution E-5 ossein gelatin 66.5 g distilled water 4747 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution
0.625 ml solution L-5 emulsion (Em-1) 200 ml aqueous solution containing 0.03 mol potassium iodide per mol

[0110]

[Table 5]

(Preparation of Emulsion (Em-6) of the Present Invention) The following solution E-6 was used in place of the solution E-1 in the preparation of the comparative emulsion (Em-1), and the addition amount of silver was 15.0%. The following solution L-6 was added in 5 minutes, and the ratio of the addition rate of the solution H-2 to the addition rate of the solution H-1 during the silver halide grain growth, the addition time, pAg, etc. are shown in Table 6. The emulsion of the present invention (Em-
6) was prepared.

Solution E-6 Oscein gelatin 133 g Distilled water 3323 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight methanol Solution 1.25 ml Solution L-6 Emulsion (Em-1) 200 ml of an aqueous solution containing 0.03 mol of potassium iodide per mol.

[0113]

[Table 6]

(Preparation of Emulsion (Em-7) of the Present Invention) The following solution E-7 was used in place of the solution E-1 in the preparation of the comparative emulsion (Em-1), and the solution additions F-1 and G were used. -1
The following solutions F-7 and G-7 were used instead of each other, and the following solution L-7 was added in 30 seconds at the silver amount of 15.0%, and the solution F-7 during the growth of silver halide grains was added. An emulsion (Em-7) of the present invention was prepared in exactly the same manner except that the ratio of the addition rate of the solution H-2 to the addition rate, the addition time, pAg and the like were controlled as shown in Table 7.

Solution E-7 Oscein gelatin 95.0 g Distilled water 4747 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution 1.25 ml solution F-7 3.0 N silver nitrate aqueous solution solution G-7 3.0 N potassium bromide aqueous solution solution L-7 emulsion (Em-1) containing 4.0% by weight of gelatin 0.01 mole potassium iodide per mole. 200 ml of aqueous solution

[0116]

[Table 7]

(Preparation of Emulsion (Em-8) of the Present Invention) In preparation of the comparative emulsion (Em-1), the following solution E-8 was used in place of the solution E-1, and the solutions F-1 and G- The following solutions F-8 and G-8 were used instead of 1, and the following solution L-8 was added in 3 minutes at the time when the amount of added silver was 15.0%.
Further, the ratio of the addition rate of the solution H-2 to the addition rate of the solution F-8 during the silver halide grain growth and the addition time, pAg
An emulsion (Em-8) of the present invention was prepared in exactly the same manner except that the above were controlled as shown in Table 8.

Solution E-8 Oscein gelatin 95.0 g Distilled water 9494 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution 0.94 ml solution F-8 2.0N silver nitrate aqueous solution G-8 3.0N potassium bromide aqueous solution containing 2.0% by weight gelatin L-8 emulsion (Em-1) 0.01 mol of potassium iodide per mol 200 ml of aqueous solution

[0119]

[Table 8]

(Preparation of Twin Seed Emulsion (TEm-2)) A spherical seed emulsion (TEm-2) was prepared by the following method.

Solution A-2 Oscein gelatin 150 g Potassium bromide 690 g Potassium iodide 24 g Water 7.2 liter Solution B-2 Silver nitrate 900 g Water 6 liter Potassium bromide 690 g Solution C- 21 1-phenyl-5-mercaptotetrazole 0.3 g to a solution a-2 was stirred vigorously at 3l 40 ° C. at 3l silver nitrate 900g solution D-2 aqueous ammonia equivalents water in water solution B-2 was added at 20 seconds, and the generation of nuclei. After 45 seconds Solution C-2 was added over 60 seconds. After another 45 seconds, Solution D-2 was added over 20 seconds and aged for 2 minutes. Ammonia concentration during aging is 0.
The concentration was 55 mol / liter, and the potassium bromide concentration was 0.060 mol / liter.

After that, the pH was adjusted to 6.0, and desalting and washing with water were immediately performed. When this seed emulsion was observed with an electron microscope,
It was a spherical emulsion having an average grain size of 0.32 μm.

(Preparation of Emulsion (Em-9) of the Present Invention) The following solution E-9 was used in place of the solution E-2 in the preparation of the comparative emulsion (Em-2), and the addition amount of silver was 15.0%. The following solution L-9 was added in 30 seconds, the following solution K-9 was used in place of the solution addition K-2, and the solution H-2 was added to the addition rate of the solution F-2 during the growth of silver halide grains. In the same manner as in the emulsion of the present invention (Em-
9) was prepared.

Solution E-9 Oscein gelatin 95.0 g Distilled water 4747 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution 1.25 ml solution L-9 emulsion (Em-2) Aqueous solution containing 0.01 mol potassium iodide per mol 200 ml solution K-9 type emulsion (TEm-2) 0.372 mol

[0125]

[Table 9]

(Preparation of Emulsion (Em-10) of the Present Invention) The following solution E-10 was used in place of the solution E-2 in the preparation of the comparative emulsion (Em-2), and the addition amount of silver was 15.0%. The following solution L-10 was added in 3 minutes, and the ratio of the addition rate of the solution H-2 to the addition rate of the solution F-2 during the silver halide grain growth, addition time, pAg, etc. are shown in Table 10. The emulsion of the present invention (Em
-10) was prepared.

Solution E-10 Oscein gelatin 190.0 g Distilled water 9494 ml HO (CH ₂ CH ₂ O) _m (CHCH ₃ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 20% by weight Methanol solution 0.625 ml solution L-10 emulsion (Em-2) Aqueous solution containing 0.01 mol potassium iodide per mol 200 ml

[0128]

[Table 10]

(Preparation of Twin Crystal Emulsion (TEm-3)) In preparation of the twin crystal emulsion (TEm-1), solution B and solution C were added for 5 minutes, and pBr during addition was adjusted. 1.80-1.9
Twin seed emulsion (TEm-3) in the same manner except keeping at 0
Was prepared. The average grain size of this seed emulsion was 0.232 μm.

(Preparation of Emulsion (Em-11) of the Present Invention) In preparation of the comparative emulsion (Em-2), the above solution E-3 was used in place of the solution E-2, and the following was used instead of the solution K-2. Solution K-11 of Example 1 was used, and at the time when the amount of added silver was 15.0%, the following solution L-11 was added for 30 seconds, and solution H-2 was added to the addition rate of solution F-2 during the growth of silver halide grains. The emulsion of the present invention (Em-1) was used in exactly the same manner except that the ratio of addition rate, addition time, pAg and the like were controlled as shown in Table 3 above.
1) was prepared.

Solution L-11 Emulsion (Em-2) Aqueous solution containing 0.06 mol of potassium iodide per mol 200 ml Solution K-11 seed emulsion (TEm-3) 0.130 mol (Twin seed emulsion (TEm-4) Preparation) A spherical seed emulsion (TEm-4) was prepared by the method described below.

Solution A-4 ossein gelatin 150 g Potassium bromide 53.1 g Potassium iodide 24 g Water 7.2 liter solution B-4 Silver nitrate 1.8 kg Water 6 liter solution C-4 Potassium bromide 1327 g 1-phenyl-5-mercaptotetrazole (Dissolved in methanol) 0.3g Water 3l Solution D-4 Ammonia water (28%) 705ml Solution A-4 and solution C-4 were vigorously stirred at 40 ° C for 30 seconds by double jet method. Was added to generate nuclei. The pBr at this time was 1.09 to 1.15.

After 1 minute and 30 seconds, D-4 was added in 20 seconds and the mixture was aged for 5 minutes.

After that, the pH was adjusted to 6.0, and desalting and washing with water were immediately performed. When the seed particles were observed with an electron microscope,
It was a spherical emulsion having an average grain size of 0.36 μm and a coefficient of variation of 23%.

(Preparation of Emulsion (Em-12) of the Present Invention) In the preparation of the comparative emulsion (Em-2), the above solution E-9 was used in place of the solution E-2, and the addition amount of silver was 15.0%. Then, the above solution L-11 was added in 30 seconds, the following solution K-12 was added instead of the solution addition K-2, and the solution F-2 was added to the solution F-2 during the silver halide grain growth. An emulsion (Em-12) of the present invention was prepared in exactly the same manner except that the ratio of H-2 addition rate, addition time, pAg and the like were controlled as shown in Table 9 above.

Solution K-12 seed emulsion (TEm-4) 0.372 mol (Preparation of twin seed emulsion (TEm-5)) A spherical seed emulsion (TEm-5) was prepared by the following method.

Solution A-4 Oscein gelatin 150 g Potassium bromide 53.1 g Potassium iodide 24 g Water 7.2 l Solution B-4 Silver nitrate 1.8 kg Water 6 l Solution C-4 Potassium bromide 1327 g 1-phenyl-5-mercaptotetrazole (Dissolved in methanol) 0.3 g with water 3 l Solution D-4 Ammonia water (28%) 705 ml While vigorously stirring solution A-4 at 40 ° C., solution B-4 and solution C-4 were applied by the double jet method for 50 seconds. Was added to generate nuclei. At this time, pBr was kept at 0.95 to 1.00.

After 1 minute and 30 seconds, the solution D-4 was added in 20 seconds and aging was carried out for 5 minutes.

After that, the pH was adjusted to 6.0, and desalting and washing with water were immediately performed. When the seed particles were observed with an electron microscope,
It was a spherical emulsion having an average grain size of 0.37 μm and a coefficient of variation of 24%.

(Preparation of Emulsion (Em-13) of the Present Invention) In the preparation of the comparative emulsion (Em-2), the above solution E-9 was used in place of the solution E-2, and the addition amount of silver was 15.0%. Then, the above solution L-11 was added in 30 seconds, the following solution K-13 was added in place of the solution addition K-2, and the solution with respect to the addition rate of the solution F-2 during silver halide grain growth was added. An emulsion (Em-13) of the present invention was prepared in exactly the same manner except that the ratio of H-2 addition rate, addition time, pAg and the like were controlled as shown in Table 9 above.

Solution 13 seed emulsion (TEm-5) 0.372 mol (Preparation of twin seed emulsion (TEm-6)) A spherical seed emulsion (TEm-6) was prepared by the following method.

Solution A-4 Oscein gelatin 150 g Potassium bromide 53.1 g Potassium iodide 24 g Water 7.2 l Solution B-4 Silver nitrate 1.8 kg Water 6 l Solution C-4 Potassium bromide 1327 g 1-phenyl-5-mercaptotetrazole (Dissolved in methanol) 0.3g Water 3l Solution D-4 Ammonia water (28%) 705ml Solution A-4 and solution C-4 were vigorously stirred at 40 ° C for 30 seconds by double jet method. Was added to generate nuclei. At this time, pBr was kept at 0.95 to 1.00.

After 1 minute and 30 seconds, the solution D-4 was added in 20 seconds and the mixture was aged for 5 minutes.

After that, the pH was adjusted to 6.0, and desalting and washing with water were immediately performed. When the seed particles were observed with an electron microscope,
It was a spherical emulsion having an average grain size of 0.34 μm and a coefficient of variation of 22%.

(Preparation of Emulsion (Em-14) of the Present Invention) In the preparation of the comparative emulsion (Em-2), the above solution E-12 was used in place of the solution E-2, and the amount of silver added was 15.0%. The above solution L-11 was added in 30 seconds, the following solution K-14 was added in place of the solution addition K-2, and the solution F-2 was added to the solution F-2 during the growth of silver halide grains. An emulsion (Em-14) of the present invention was prepared in exactly the same manner except that the ratio of H-2 addition rate, addition time, pAg and the like were controlled as shown in Table 9 above.

Solution 14 type emulsion (TEm-6) 0.372 mol (Preparation of emulsion (Em-15) of the present invention) Comparative emulsion (Em-
In the preparation of 2), instead of the solution E-2, the above solution E-
3 and the amount of added silver was 15.0%, the following solution L-
15 is added for 30 seconds, and the ratio of the addition rate of the solution H-2 to the addition rate of the solution F-2 during silver halide grain growth, the addition time, pAg, etc. are controlled as shown in Table 3 above. The emulsion of the present invention (Em-1
5) was prepared.

Solution L-15 Emulsion (Em-2) 100 ml of an aqueous solution containing 0.05 mol of potassium iodide per mol (Preparation of emulsion (Em-16) of the present invention) Comparative emulsion (Em-
In the preparation of 2), instead of the solution E-2, the above solution E-
3 and the amount of added silver was 15.0%, the following solution L-
16 is added for 30 seconds, and the ratio of the addition rate of the solution H-2 to the addition rate of the solution F-2 during the silver halide grain growth, the addition time, pAg, etc. are controlled as shown in Table 3 above. The emulsion of the present invention (Em-1
6) was prepared.

Solution L-16 Emulsion (Em-2) 100 ml of an aqueous solution containing 0.04 mol of potassium iodide per mol (Preparation of emulsion (Em-17) of the present invention) Comparative emulsion (Em-
In the preparation of 2), instead of the solution E-2, the above solution E-
3 and the amount of added silver was 15.0%, the following solution L-
17 is added for 30 seconds, and the ratio of the addition rate of solution H-2 to the addition rate of solution F-2 during silver halide grain growth, addition time, pAg, etc. are controlled as shown in Table 3 above. The emulsion of the present invention (Em-1
7) was prepared.

Solution 17 100 ml of an aqueous solution containing 0.025 mol of potassium iodide per mol of emulsion (Em-2) (Preparation of emulsion (Em-18) of the present invention) Comparative emulsion (Em-
In the preparation of 2), instead of the solution E-2, the above solution E-
3 and the amount of added silver was 15.0%, the following solution L-
18 is added for 30 seconds, and the ratio of the addition rate of the solution H-2 to the addition rate of the solution F-2 during the silver halide grain growth, the addition time, pAg, etc. are controlled as shown in Table 3 above. The emulsion of the present invention (Em-1
8) was prepared.

Solution 18 Aqueous solution containing 0.015 mol of potassium iodide per mol of emulsion (Em-2) 100 ml Emulsions (Em-1) to (Em-18) During the growth of tabular silver halide grains and at the final stage. The tabular silver halide grains thus obtained and the circle-equivalent diameter of the projected area in the direction perpendicular to the principal plane were observed with an electron microscope and the rate of change of the circle-equivalent diameter was examined. ) ~ (Em-
Regarding 18), it was found that the silver halide grains when the amount of added silver was about 20% corresponded to the tabular base silver halide grains in the present invention. Emulsions (Em-3) to (Em-18) were found to be substantially predominant in the tomographic planes of tabular silver halide grains prepared by using a diamond cutter, from the point analysis of the silver halide composition using the EPMA method. It was shown to have a layered structure parallel to the plane.

Emulsions (Em-1) to (Em-18) are shown in Tables 11 and 12.
The characteristics of

[0152]

[Table 11]

[0153]

[Table 12]

A silver halide emulsion (Em-1) was formed on a transparent triacetate cellulose film support which had been subjected to subbing processing.
To (Em-18) were applied as follows to prepare a light-sensitive material.

5 g of the following magenta coupler (M-1),
0.95 g of the following colored magenta coupler (CM-1) and 0.10 g of the following DIR coupler (D-1) were dissolved in 5 cc of dibutyl phthalate, and 8 cc of 1.0% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) was dissolved. And 70% of 5% gelatin aqueous solution were mixed and emulsified and dispersed by a colloid mill.

[0156]

[Chemical 1]

The dispersion liquid obtained as described above and (Em-
Each of 1) to (Em-18) was mixed with 350 g (including 40 g of silver) emulsion which was optimally sensitized with sulfur, gold and green, to give a silver amount of 16 mg / dm ² . Was applied as follows.

Next, a protective layer containing 2.3 g (per 1 m ² ) of gelatin was coated on the surface of the plate to give Sample Nos. 11 to 28.

These samples, after being stored under the following conditions A, were subjected to sensitometric exposure with white light and processed in the following processing steps to evaluate sensitivity and RMS granularity. Also, in order to evaluate the pressure resistance of each sample, after bending each sample along a cylinder with a diameter of 4 mm,
Similarly, it was exposed and developed.

(Conditions) A: 4 days at 65 ° C. and 30% RH Treatment step (38 ° C.) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water wash 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in each processing step is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter and adjust to pH 10.0.

<Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter and pH was adjusted to pH 6. Adjust to 0.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 cc Conidax (Konica Corporation) 7.5 cc Add water to make 1 liter.

The relative sensitivity (S) is the fog density +0.1.
Is the relative value of the reciprocal of the amount of received light that gives the concentration of, and is shown as a value where the sensitivity of Sample 11 is 100.

The RMS value is 1000 times the standard deviation of the fluctuation of the density value which occurs when the density of the minimum density + 1.0 is scanned by a micro decimator with an aperture scanning area of 250 μm ^2.
The RMS value of 100 is shown as a value.

The change in the density of the pressed part due to bending was measured by measuring the density of the pressed part and the density of the unpressurized part with a microdecimator at the density point where the fog density was +0.15. Part 11 Change in concentration was calculated as follows, and
The value is shown as a relative value (change in relative density of the pressurizing portion) with the value of 100 as 100.

Change in density of pressed part = | (concentration of pressed part−concentration of unpressurized part) /0.15|×100 (%) Table 13 uses silver halide emulsions (Em-1) to (Em-18) The evaluation results of the relative density change, the RMS granularity, and the pressure part relative density change for the prepared sample Nos. 11 to 28 are shown.

[0169]

[Table 13]

From Table 13, Sample Nos. 13 to 25 using the silver halide photographic emulsions (Em-3) to (Em-15) of the present invention are as follows.
Comparative emulsions (Em-1), (Em-2), (Em-16) to (Em
-18) Sample No.11, No.12, No.26, No.27, No.2
8, excellent performance was shown in all of sensitivity, RMS granularity, and change in relative density of pressure portion.

Example 2 Silver halide emulsions (Em-1) prepared in Example 1 to
(Em-18) was optimally chemically sensitized. Each of these emulsions is designated as (emulsion D) in the following sample formulation to prepare a multilayer color light-sensitive material sample.

First, layers having the following compositions were sequentially formed on the triacetyl cellulose film support from the support side.

First layer alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Second layer diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg (silver halide color light-sensitive material) Preparation) Each layer having the composition shown below was provided on the above-mentioned transparent support to prepare samples 101 to 118 which are multilayer color light-sensitive materials.

[0174] The coating amount (Composition of photosensitive layer) The silver halide and colloidal silver, the amount expressed in terms of metallic silver in the unit of g / m ^2, also, the coupler, the additive g / m ²
The amount expressed in units is also shown for the sensitizing dye in terms of the number of moles per mole of silver halide in the same layer.

Sample 101 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High Boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye ( SD-2) 1.4 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing dye (SD-4) 0.7 × 10 ^-4 cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) ) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Medium-sensitive red sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD- 1) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 -4 sensitizing dye (SD-3) 1.15 × 10 -5 sensitizing dye (SD 4) 0.86 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling solvent (OIL-1) 0.16 Gelatin 0.79 Fifth Layer: High Sensitivity Red Sensitive layer Emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ^-4 Sensitizing dye (SD-2) 1.0 × 10 ^-4 Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-2 ) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity green sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M- 1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium-sensitive green sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 ^-4 Sensitizing dye (SD-8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 Layer 10: High sensitivity green sensitive layer Emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 ^-5 Sensitizing dye (SD-7) 7.1 × 10 ^-5 Sensitizing dye (SD-8) 7.1 × 10 ^-5 Magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 12th layer: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^{− 5} Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point solvent (OIL-2) 0.42 Gelatin 1.40 13 layers: high-sensitivity blue-sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Alkali soluble Tsu preparative agents in addition to the (average particle diameter 2 [mu] m) 0.15 Polymethyl methacrylate (average particle size 3 [mu] m) 0.04 Slip agent (WAX-1) 0.04 Gelatin 0.55 In addition the compositions, coating aid Su-1, dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

The emulsions used in the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0177]

[Table 14]

The sample was applied by a multi-slide hopper type coater at the first time, and the first to eighth layers were simultaneously applied, and at the second time, the ninth to 16th layers were simultaneously applied thereon.
Sample 101 had a silver coating amount of 6.25 g / m ² , a dry film thickness of 18 μm, and a specific photographic sensitivity of 420.

[0179]

[Chemical 2]

[0180]

[Chemical 3]

[0181]

[Chemical 4]

[0182]

[Chemical 5]

[0183]

[Chemical 6]

[0184]

[Chemical 7]

[0185]

[Chemical 8]

[0186]

[Chemical 9]

[0187]

[Chemical 10]

[0188]

[Chemical 11]

[0189]

[Chemical 12]

These samples were exposed to sensitometric exposure with white light and processed in the following processing steps to evaluate sensitivity.

In order to evaluate the pressure resistance of each sample, after bending each sample along a cylinder having a diameter of 4 mm,
Similarly, it was exposed and developed.

Treatment process (38 ° C) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Each treatment The composition of the treatment liquid used in the process is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter and adjust to pH = 10.0.

<Bleach> Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and pH was adjusted to 6.0 using ammonium water. To do.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution)
1.5 ml Konidax (Konica Corporation) 7.5 ml Add water to make 1 liter.

Regarding the sensitivity, the relative value of the reciprocal of the received light amount giving the density of fog +0.1 was used, and the sensitivity of Sample No. 101 was set to 100 as a relative value.

The RMS granularity was 1000 times the fluctuation of the density value produced when the density of the maximum density +1.0 was scanned by a microdensitometer with an aperture scanning area of 250 μm ² ,
It was shown as a relative value with the RMS value of o.101 as 100.

The change in the density of the pressed part due to bending was measured by a microdensitometer for the density of the pressed part and the density of the unpressurized part at the density point of fog density + 0.15.
The concentration change value of each sample was obtained by the following, and shown as a relative value (relative concentration change of the pressure portion) with the value of Sample No. 101 being 100.

Change in density of pressed part = | (concentration of pressed part−concentration of unpressurized part) /0.15|×100 (%) Table 15 uses silver halide emulsions (Em-1) to (Em-18) The results of evaluation of relative sensitivity, RMS granularity, and change in relative density of the pressure portion are shown for the prepared sample Nos. 101 to 118.

[0201]

[Table 15]

From Table 15, sample Nos. 103 to 115 using the silver halide photographic emulsions (Em-3) to (Em-15) of the present invention are shown.
Are comparative emulsions (Em-1), (Em-2), (Em-16).
~ (Em-18) sample No. 101, No. 102, No. 116 ~ N
Excellent performance was exhibited in all of sensitivity, RMS granularity, and change in relative density of the pressure portion at o.118.

[0203]

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a silver halide photographic emulsion which gives a photographic light sensitive material having high sensitivity, excellent graininess and improved pressure resistance, and a silver halide photographic light sensitive material using the same. be able to.

Claims (4)

[Claims] 1. A silver halide photographic emulsion containing silver halide grains and a dispersion medium, wherein the silver halide grains contained in said silver halide photographic emulsion are tabular silver halide grains, and said tabular halogenated. A silver halide characterized in that silver particles have a layered structure substantially parallel to the principal plane, and 50% or more (number) of the tabular silver halide grains have 10 or more dislocation lines per grain. A silver halide photographic emulsion containing grains. 2. A silver halide photographic emulsion according to claim 1, wherein the tabular silver halide grains have two twin planes substantially parallel to the principal plane. 3. The silver halide photographic emulsion according to claim 2, wherein the tabular silver halide grains are monodisperse. 4. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is one of claim 1, 2 or 3. 1. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion of.